Polymers
with hydrolyzable groups in their backbones have numerous
potential applications in biomedicine, lithography, energy storage,
and electronics. In this study, acetal and ester functionalities were
incorporated into the backbones of copolymers by means of alternating
ring-opening metathesis polymerization catalyzed by the third-generation
Grubbs ruthenium catalyst. Specifically, combining large-ring (7–10
atoms) cyclic acetal or lactone monomers with bicyclo[4.2.0]oct-1(8)-ene-8-carboxamide
monomers provided perfectly alternating copolymers with acetal or
ester functionality in the backbones and low to moderate molecular
weight distribution (D̵
M = 1.2–1.6).
Copolymers containing ester and acetal backbones hydrolyzed to significant
extent under basic conditions (pH 13) and acidic conditions (pH ≤
5), respectively, to yield the expected byproducts within 30 h at
moderate temperature. Unlike the copolymer with an all-carbon backbone,
copolymers with a heteroatom-containing backbone exhibited the viscoelastic
behavior with crossover frequency, which decreases as the size of
the R group on the acetal increases. In contrast, the glass transition
temperature (T
g) decreases as the size
of the R group decreases. The rate of hydrolysis of the acetal copolymers
was also dependent on the R group. Thus, ruthenium-catalyzed alternating
ring-opening metathesis copolymerization provides heterofunctional
copolymers whose degradation rates, glass transition temperatures,
and viscoelastic moduli can be controlled.